Aerosol textile sizing product and method

ABSTRACT

AEROSOL AQUEOUS SIZING PRODUCTS CHARACTERIZED IN PROVIDING HIGHLY VARIABLE AMOUNTS OF STIFFNESS ARE PROVIDED, COMPRISING POLYVINYLPRROLIDONE HAVING AN AVERAGE MOLECULAR WEIGHT OF ABOUT 10,000 TO 400,000 ALONG WITH A WATER-SOLUBLE SILOXANE-OXYALKYLENE BLOCK COPOLYMER.

March 27, 1973 R. c, STEINHAUER ET AL 3,723376 AEROSOL TEXTILE SIZINGPRODUCT AND METHOD Filed Oct. 5, 1970 PERCENT ST/FFNESS INC REA SE//\/VE/\/TORS ROGER C. STE/NHAUER LEONARD A. FALEV/TCH DAVID R. CHURCHBY awe/fa ATT).

lWOLIFfiULA/i WEIGHT IN THOUSANDS United States Patent O 3,723,376AEROSOL TEXTILE SIZING PRODUCT AND METHOD Roger C. Steinhauer, 291Dogwood, Park Forest, II]. 60466; Leonard A. Falevitch, 5932 Peck Ave.,La Grange, Ill. 60525; and David R. Church, 188 Dogwood, Park Forest,Ill. 60466 Filed Oct. 5, 1970, Ser. No. 77,968 Int. Cl. C081? 33/04,33/08 U.S. Cl. 26029.6 HN 12 Claims ABSTRACT OF THE DISCLOSURE Aerosolaqueous sizing products characterized in providing highly variableamounts of stiffness are provided, comprising polyvinylpyrrolidonehaving an average molecular weight of about 10,000 to 400,000 along witha water-soluble siloxane-oxyalkylene block copolymer.

This invention relates to compositions and methods for textile sizing.More particularly, it relates to aqueous compositions in aerosol formfor sizing textile fabrics.

It is known for manufacturers of textile fabrics to size the fabricsprior to sale in order to improve the body thereof, and to generallyimprove the appearance and wearing qualities of the textiles. Sizingproducts are generally applied by dipping the fabric into baths. Suchsizing products are eventually removed from the fabric, due tolaundering and wear. In the case of many fabrics, the housewife appliesstarch as part of the laundering and ironing process to restore thedesirable qualities of sizing products to the fabric.

The last ten years or so have seen the development of starch into anaerosol product. However spray starch suffers certain disadvantages suchas imparting too much stiffness which many consumers dislike. n theother hand, attempts to formulate other sizing agents into aerosolproducts for household use have not been entirely successful.

If the problems of aerosol packaging are overcome the product usuallydoes not impart sufficient stiffness so as to compare to starch. US.Pat. 3,068,120 teaches an aerosol sizing composition using an aqueoussolution of sodium carboxymethylcellulose. Using sodium CMC as thesizing resin does not allow the formulation of a product which willapproach the stiffness of starch. Thus although the body, softness andfeel of fabrics are improved by such a product, sufficient stiffness isnot imparted which is desired by many users.

Thus it is an object of this invention to provide an aerosol aqueoussizing composition. Another object and advantage of this invention is toprovide an aerosol sizing composition which can be formulated to providea highly variable amount of stiffness to the fabric. Yet another objectand advantage of this invention is to provide an aerosol aqueous sizingcomposition which will impart de sirable qualities to the fabriccomparable or superior to those obtained through the use of starch.

In a specific embodiment, the compositions of this invention may beexemplified by an aqueous sizing composition comprising, by weight,about 0.1 to about 3% of polyviriylpyrrolidone having an averagemolecular weight of about 10,000 to about 400,000; about 0.1 to about 1%of a water-soluble siloxane-oxyalkylene block copolymer such as UnionCarbides L-520; about 4 to about of propellant and the remainder beingwater. The composition may also contain about 0.1-1%, and preferablyabout 0.4% of a defoamer such as a silicone such as SAG 470 silicone inorder to aid in penetration of the fabric. In addition, the compositionmay also contain from about 0.1-1%, and preferably about 0.2% of agermicide. An

ice

especially preferred germicide is a combination of 2,4,4-trichloro-2'-hydroxy diphenyl ether with mixed alkyl dimethylethylbenzyl and alkyl dimethyl benzyl ammonium chlorides where the alkylcontains 12-18 carbon atoms. A corrosion inhibitor system may also beincorporated in an amount of about 0.01-0.5%, and preferably about 0.10%as is well known in the art of aerosol packaging. Suitable corrosioninhibitors include among others urea, sodium benzoate andtriethanolamine in the amounts as set forth above. In addition variableamounts, such as about 0.1-1.0%, and preferably about 0.5% of apolyethylene glycol, may be added to impart a desired hand to thefabric. Other optional ingredients may be added such as preservatives,about 0.1-0.8% and preferably about 0.2%; and a suitable perfumegenerally in an amount of about OBI-0.02%.

The product of this invention may be applied to any synthetic textilefabric, such as Orlon, Dacron, and nylon for example. In addition it maybe applied to natural fabrics such as silk, flannel, linen, cotton andfelt.

The polyvinylpyrrolidone (PVP) component may be any homopolymer obtainedby addition polymerization of a vinyl pyrrolidone monomer such asN-vinyl-2-pyrrolidone and the like, said polymer having an averagemolecular weight from about 10,000 to about 400,000.Polyvinylpyrrolidone is commercially available in molecular weights of10,000, 40,000, 160,000, 360,000 and in higher molecular weight groupsas well as in blends of the foregoing. It has been found that increasingthe molecular weight of the PVP used in the product of this inventionover certain ranges permits a high degree of flexibility in makingsizing products which possess a rather wide range of stiffnessproperties. As the molecular Weight of the resin is increased from 1,000to 60,000 there is a sharply rising increase in stiffness imparted tothe fabric as is illustrated in the attached drawing. The attacheddrawing is a graph depicting the effect of PVP molecular weight on thestiffness of polyester/cotton blend fabric using ASTM test methodD-1388-64. In the graph the percentage stiffness increase over water(ordinate) has been plotted against the average molecu lar weight (inthousands) of the polyvinylpyrrolidone (abscissa). The dotted lines Aand B show the results with a commercial aerosol starch product and witha commercial aerosol sodium CMC product respectively. The curved line Cshows the increased stiffness imparted as the molecular weight PVP usedincreases. From line C it can be seen that the greatest variation instiffness occurs from about 15,000: molecular weight to about 140,000molecular weight, then levels off. Thus the use of the lower molecularweight PVP, i.e. having a molecular weight of about 10,000 to about40,000 is preferred to impart a light to medium stiffness upon theapplication of the product. The use of a PVP having a molecular weightof about 160,000 is preferred to impart a stiffness comparable tostarch. The concentration of a given molecular weight of PVP in theproduct also affects the stiffness of the resultant finish imparted tothe fabric. Using a PVP having an average molecular weight of about40,000 at a concentration of about 1.2% or more in the product achievesa starch-type stiffness; a concentration of about 0.282% of the same PVPprovides a mild stiffness similar to those products utilizing sodiumcarboxymethylcellulose.

The composition of the present invention contains as a second essentialcomponent a water-soluble siloxaneoxyalkylene block copolymer, orsilicone fluid. Suitable water-soluble silicone fluids for use in thepractice of the present invention are those with surface activeproperties, which embody the properties of both organic and siliconeoils and impart good lubrication and anti-wear properties to variousproducts, and are such as those disclosed in US. Pat. No. 2,834,748 andUS. Pat. No. 3,140,198. A particularly preferred silicone fluid wouldalso have an average viscosity in centistokes at 25 C. of approximately1,100 and an apparent specific gravity, 25/25 C. of 1.03. Suitablewater-soluble silicone fluids for use in the present invention arecommercially available from Union Carbide, such as Silicone L-520.

The specific propellant component is not critical, and suitable volatileliquid propellants are well known in the art. The propellant may be, forexample, the partially fluorinated, or wholly fluorinated, or partiallyfluorinated-partially chlorinated, or partially fluorinated-partiallybrominated aliphatic hydrocarbons having from 1 to 2 carbon atoms suchas are available under the trademark Freon and mixtures thereof, lowboiling hydrocarbons having from 1 to 8 carbon atoms such as methane,propane, butane, their isomers, their mixtures and the like, nitrogen,nitrous oxide, carbon dioxide and the like. Because the water present inthe product of this invention suppresses flammability, it is preferredto use low boiling hydrocarbons such as butanes.

In producing the aerosol aqueous sizing products of the invention, anaerosol container equipped with a valve may be filled by the normal coldfilling method; or the propellant may be introduced by pressure fillingthrough the valve nozzle; or other known methods. In formulating, it ispreferred to add the PVP and then the silicone fluid to the water whilestirring. It is particularly preferred to pre-blend any additionalcomponents before adding them; for example, by admixing the germicidesif liquid, adding thereto the preservative, and then adding a preblendedperfume and nonionic surfactant and finally adding this total mixture tothe water, PVP and silicone fluid. Thereafter the corrosion inhibitor ifany may be added.

Reference will now be made to specific examples of particularcompositions of the invention.

EXAMPLE I The following formulation was filled into metal aerosol cans,utilizing Newman-Green valves and actuators:

Percent by weight Ingredient: in can Polyvinylpyrrolidone, averagemolecular wt.

Alkoxylated organosilicone copolymer (water sol., viscosity 25 C. of1,100; specific gravity at 25 C. of 1.03) 0.3 Methyl dodecyl benzyltrimethyl ammonium chloride and methyl dodecyl xylene bis (trimethylammonium chloride)preservative 0.009 Polyethylene glycol averagemolecular wt. 200 0.564 Urea-corrosion inhibitor 0.047 Hydrophobicsilicone fluid (Sag 470)-antifoam agent 0.038 Alkyl dimethyl ethylbenzylammonium chloride and alkyl dimethyl benzyl ammonium chloridegermicide0.094 2,4,4 trichloro-2-hydroxy diphenyl ether germicide 0.009Perfume/nonionic surfactant in 1/1 ratio 0.038 Isobutane propellant6.000

Water, remainder to 100%.

The above formulation was stable through seven freeze-thaw cycles andpasses a two week 125 F. high temperature stability test. A panel testwas conducted wherein each panel member was assigned six whitepolyester/ cotton men's dress shirts. The panel members wore each shiftone day then the shirt was washed and refinished with either the productabove or a commercial aerosol sizing product that incorporated sodiumCMC and an aerosol starch product for comparison purposes. The aboveformulation was found to be comparable in stiffness of the aerosolstarch product.

4 EXAMPLE n A series of formulations using 1.5% aqueous solutions of PVPhaving average molecular weights of 10,000 (K15); 40,000 (K30);160,000(K60); and 360,000 (K) respectively were prepared and filled inaerosol containers as set forth above using 6% isobutane propellant andno additional ingredients. Unsatisfactory spray streamer patternsresulted. About 0.3% watersoluble alkoxylated organosilicone copolymer(Silicone L-520) was added to each and a satisfactory pattern resulted.Another series containing 0.45% of each of the various molecular weightPVP and about 0.3% Silicone L-520 were sprayed onto polyester/cottonbatiste shirt fabric and compared with a commercial spray starch and acommercial spray sodium CMC sizing by the Single Cantilever test,ASTMD138864. The results are set forth in the attached drawing, fromwhich it can be seen that the stiffness imparted varies directly withthe molecular weight of the PVP. Thereby an effective sizing can beimparted at any one of the so-called light starching, moderate starchingor heavy starching levels.

EXAMPLE III The following formulation was filled into metal aerosolcans, again using Newman-Green valves and actuators:

Percent by weight Ingredient: in can PV'P, average molecular wt. 160,0001.41 Alkoxylated organosilicone copolymer (water sol.; viscosity 25 C.of 1,100; specific gravity 25 C. of 1.03) 0.282 Either urea; sodiumbenzoate; or triethanolaminecorrosion inhibitor 0.047 Polyethyleneglycol, average molecular wt.

200 0.564 Methyl dodecyl benzyl trimethyl ammonium chloride and methyldodecyl xylene bis (trimethyl ammonium chloride)preservative 0.009 Sag470 hydrophobic silicone fluid 0.376 Alkyl dimethyl ethylbenzyl ammoniumchloride and alkyl dimethyl benzyl ammonium chloridegermicide 0.0942,4,4 trichloro2-hydroxy diphenyl et.her-

germicide 0.009 Perfume 0.0188 Nonionic carrier for perfume 0.0188Modified fractions of coal tar bases as acid corrosion inhibitor 0.00094Isobutane 6.000

Water, remainder to The above formulation was freeze-thaw stable throughseven cycles, produced satisfactory spray patterns, and on panelevaluations as set forth hereinabove imparted a stiffness to fabricsequal to or greater than that of an aerosol starch product.

EXAMPLE IV Any soil repellant fluorocarbon may be added to ourcomposition to impart water and oil-based soil repellency. Suchcompounds may be the water and oil repelling fluoro-, polyfluoroandperfluorinated: -alkyl phosphates, alkanamide-alkyl phosphates,polyoxa-allcanamidoalkylanols and their phosphates, esters, etheralcohols, polyols, sulfonamido polyols, vinyl ethers and vinyl benzenes.Preferred soil repellant fluorocarbons are available under thedesignation Zonyl RP, Zepel B, TIJF-2247, and TLF- 2601.

When Zepel B, TIP-2247 and TLF-2601 were incorporated in an amount ofabout 0.010.1%, and especially about 0.04% by weight, into theformulation of Example I, consumer panel and laboratory testing showedthat excellent water and oil-stain repellency was imparted to thefabric.

While this invention has been described and exemplified in terms of itspreferred embodiments, those skilled in the art will appreciate thatvariations and modifications may be made without departing from thespirit and scope of the invention.

What is claimed is:

1. An aerosol composition comprising, by weight, about 0.1-3% ofpolyvinylpyrrolidone having an average molecular weight of about10,000-400,000; about 0.11% of a water-soluble siloxane-oxyalkyleneblock copolymer; about 410% of propellant; and water.

2. The composition of claim 1 in which said polyvinylpyrrolidone has anaverage molecular weight of about 40,000.

)3- The composition of claim 1 in which said polyvinylpyrrolidone has anaverage molecular weight of about 160,000.

4. The composition of claim 1 in which said polyvinylpyrroudone ispresent in an amount of about 1.5%.

5. The composition of claim 1 in which said siloxaneoxyalkylene blockcopol'ymer has an average viscosity at 25 C. of approximately 1,100centistokes and a specific gravity at 25 C. of 1.03.

6. The composition of claim 3 in which said siloxaneoxyalkylene blockcopolymer is present in an amount of about 0.3%.

7. The composition of claim 1 which includes about 0.010.1% of a soilrepellant fluorocarbon.

8. The composition of claim 7 in which said fluorocarbon is present inan amount of about 0.04% by weight.

9. The composition of claim 1 including mixed alkyl dimethyl ethylbenzyland alkyl dimethyl benzyl ammonium chlorides where the alkyl contains12-18 carbon atoms.

10. An aerosol composition comprising, by weight, about l-3% ofpolyvinylpyrrolidone having a molecular weight of about 10,000400,000;about 0.1-1% of a watersoluble siloxane-ox'yalkylene block copolymer;about 0.4% of defoamer; about 0.2% of germicide; about 0.02% ofcorrosion inhibitor; about 0.2% of preservative; about 0.5% of apolyethylene glycol; about 0.02% of a perfume; about 6% of isobutanehydrocarbon propellant; and the remainder water.

11. The composition of claim 10 in which said germicide is a mixture of2,4,4-trichlor0-2'-hydroxy diphenyl ether and mixed alkyl dimethylethylbenzyl and alkyl dimethyl benzyl ammonium chlorides where the alkylcontains 12-18 carbon atoms.

12. A method of sizing a textile fabric comprising spraying on saidfabric an aqueous solution of 13% of polyvinylpyrrolidone having anaverage molecular weight of about 10,000-400,000; about 0.11% of awatersoluble siloxane-oxyalk'ylene block copolymer; about 4-10% ofpropellant; and water.

References Cited UNITED STATES PATENTS 3,073,794 1/ 1963 Stoner260--33.8

3,140,198 7/1964 Dawson et a1 117-138.8

3,294,861 12/1966 Simpson 260 -827 3,502,743 3/ 1970 Wolf et al 260-851FOREIGN PATENTS 6,702,020 8/ 1968 Netherlands.

1,052,023 12/1966 Great Britain.

1,541,599 8/1968 France.

1,140,543 12/1962 Germany.

OTHER REFERENCES Ramaszeder; Magy. Textiltech. 16, 566-69 (1964).Davidson et al.; Water Soluble Resins, Reinhold, New York, 1962, p. 132.

MELVdN GOLDSTEIN, Primary Examiner US. Cl. X.R.

117-104 R, 139.5 A; 260- [29.6 NR

